NMR shifts, orbitals, and M⋯H-X bonding in d 8 square planar metal complexes

Yong Zhang, Jared C. Lewis, Robert G. Bergman, Jonathan A. Ellman, Eric Oldfield

Research output: Contribution to journalArticlepeer-review


We have investigated M⋯H-C interactions in d 8 square planar Rh and Pt complexes involving different types of C-H bonds, as well as a M⋯H-N hydrogen-bonded complex, using a combination of DFT and "atoms-in-molecules" (AIM) theory. The AIM analysis shows that both M⋯H-C and M⋯H-N interactions in d 8 square planar complexes are of a closed-shell, electrostatic nature, similar to protein backbone hydrogen bonds. However, at the shortest M⋯H distances, both interactions have partial covalence. We find no evidence for the involvement of d z 2 orbitals in M⋯H-C interactions but do find evidence for the involvement ofd xz/yz orbitals in M⋯H-C bonding. The DFT calculations reproduce well the experimental proton NMR chemical shifts, with a theory-versus-experiment correlation coefficient R 2 = 0.985. There are large downfield 1H NMR chemical shift changes on metal bonding, accompanied by changes in shielding tensor orientations.

Original languageEnglish (US)
Pages (from-to)3515-3519
Number of pages5
Issue number14
StatePublished - Jul 3 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


Dive into the research topics of 'NMR shifts, orbitals, and M⋯H-X bonding in d 8 square planar metal complexes'. Together they form a unique fingerprint.

Cite this